It is known that commercially important polyamides, such as nylon-6 and nylon-6,6, have excellent physical properties in many respects. However, for certain textile application fabrics and similar products prepared from such nylons are somewhat deficient in moisture absorption. This characteristic is important because according to ENCYCLOPEDIA OF POLYMER SCIENCE AND TECHNOLOGY, Vol. 10, Section Polyamide Fibers, moisture absorption determines comfort, ease and cost of dyeing, antistatic character and hand or feel of the fabric. To overcome this moisture absorption deficiency many attempts have been made but none have been commercially successful to date.
Disclosed herein is a novel copolymer which can be converted into a fiber having moisture absorption properties similar to that of cotton, a commercial standard of comparison. This novel copolymer consists of blocks of random poly(dioxa-amide) and blocks of polyamide. Surprisingly, the incorporation of blocks of certain random poly(dioxa-amide) with a certain polyamide does not adversely effect the many desirable fiber properties of the polyamide and yet substantially improves its moisture absorption property. Also the copolymer can be formed into a desired shape by extrusion, injecting molding and other well-known thermoplastic forming methods.
A block copolymer can result when a mixture of polymer X and polymer Y, both of which contain amides is properly processed. Thus the resulting block copolymer contains relatively long chains of a particular chemical composition, the chains being separated by a polymer of different chemical composition; thus diagrammatically ##STR1## A block copolymer can also contain relatively long chains of a particular chemical composition but in this type the chains are separated by a low molecular weight "coupling group;" thus diagrammatically ##STR2## Each of the aforementioned polymer chains, i.e., X and/or Y can be a homopolymer or a random copolymer.
Generally, copolymers containing the amide function, i.e., ##STR3## can be formed by melting two polyamides. Thus when two different polyamides are mixed and heated above their melting points they form copolymers. This process is also known as melt blending. However, the length of time the polymers are maintained at a temperature above their melting points has a profound effect on the resulting structure. As the mixing at the elevated temperature begins the molecule is a combination of blocks of random poly(dioxa-amide) and blocks of polyamide. But gradually as the heating and mixing continues the length of the blocks of polyamide decreases because more segments of the random polymer are produced. Thus if the blending and heating occurs for a sufficient time all the "blocks" disappear and mostly random sequences form as evidenced by deterioration of its physical properties including melting point. At present there is no known direct way of determining chain sequences of such a polymer. But indirect methods exist and these are discussed in detail hereinafter. Controlled decomposition of such a copolymer will yield all identifiable components that make up the copolymer but will not indicate sequence.
Polymers, including copolymers, containing amide functional groups generally result from a reaction known as condensation. Condensation refers to a polymer forming reaction in which water can be a by-product. The various types of polymers that can be produced from condensation (or step growth polymerization) are described hereinafter. The initial stage of a condensation polymerization consists of random combinations of two monomeric units to form dimer molecules. Examples of these could be the formation of two units of nylon-11 from the corresponding amino acid (11-aminoundecanoic acid) in the case of an AB polyamide ##STR4## or adipic acid molecule and hexamethylene diamine in an AABB system ##STR5## The letter "A" refers to one of the functional groups of the monomer, "B" refers to the other.
The foregoing dimer molecules will combine with equal facility with another monomeric unit or a dimer unit. In this fashion, the average degree of polymerization (DB) builds during the course of the reaction. This is discussed in greater detail in ORGANIC CHEMISTRY OF SYNTHETIC HIGH POLYMERS, Robert W. Lenz, Library of Congress Catalog Card No. 66-22057.
In this same manner, as reactions I and II, random copolymers can be formed. The only condition necessary is that more than one type (or two if an AABB system is used) of monomer unit be present during the condensation reaction. Thus following from the example above where monomers of AB and AABB polymers are present in the same reactor at the beginning of the polymerization, the AB monomer (amino acid) will react with a similar unit or the AABB monomer unit (the diamine or diacid) in a random fashion since their reactivities are similar. The final result of such a polymerization will be a random copolymer. If their reactivities are very dissimilar, there would be a tendency to become blocks, however, units having similar carboxylic and/or similar amine ends have similar reactivities. Further examples of random copolymers are given in U.S. Pat. No. 3,397,107 where the monomer units of nylon 303/T and caprolactam are polymerized in a random fashion. Another example is contained in U.S. Pat. No. 3,594,266 in which a polyethylene oxide diamine, terephthalic acid and caprolactam were polymerized in a random fashion. Since the condensation polymerization is a random sequence of events it would be extremely improbable to obtain an alternating copolymer using dissimilar monomer units in the condensation reaction as it is known today. An alternating copolymer can be classified as a special type of random copolymer.
Formation of a condensation block copolymer cannot be easily achieved using the conditions described heretofore because of the random reaction of monomeric units. Block copolymer preparations have been described in the patent literature using at least two techniques. One technique, as described before, is melt blending two homopolymers at temperatures where the polyamide becomes reactive to amide interchange, chain extension and hydrolysis. Such a technique is disclosed in U.S. Pat. No. 3,393,252. When the conditions are closely controlled block copolymers with long sequence lengths can be optimized even though a certain amount of amide interchange occurs to form an insignificant amount of random sequences.
Another method of preparing block copolymers has been described in U.S. Pat. No. 3,683,047. It consists of polymerizing two homoprepolymers of molecular weight from 1000 to 4000. In this specific case, one prepolymer was carboxyl terminated while the other was amine terminated. The result of the polymerization is a block copolymer. Under the conditions of polymerization very little randomization occurred as indicated by little loss in melting point during the blend time. These block copolymers have been called ordered copolymers since by the nature of the starting materials reactive functional groups they cannot react with themselves.
Examples of random copolymers are as follows: CHEMICAL ABSTRACT 88764f, Vol. 70, 1969, (Japanese Pat. No. 28,837/68) discloses a copolymer prepared from the combination of (a) salt of bis-(.alpha.-aminopropoxy)ethane (also referred to as 30203) and adipic acid and (b) the monomer caprolactam. British Patent 1,169,276 discloses a random copolymer having improved hydrophilic properties prepared from the combination of (a) salt (I) of H.sub.2 N(CH.sub.2).sub.3 --O--CH.sub.2 --C(CH.sub.3).sub.2 --CH.sub.2 O--(CH.sub.2).sub.3 NH.sub.2 and adipic acid and (b) the monomer caprolactam; also a random copolymer of the aforementioned salt (I) and hexamethylene diammonium adipate [H.sub.3.sup.+ N(CH.sub.2).sub.6 NHCO(CH.sub.2).sub.6 CO.sup.- ] also referred to as nylon-6,6 salt. CHEMICAL ABSTRACT 4514h, Vol. 49, 1955, discloses a random copolymer prepared from the (a) salt (II) of H.sub.2 N(CH.sub.2).sub.3 -O-(CH.sub.2).sub.3 --NH.sub.2 and adipic acid and (b) nylon-6,6 salt. Salt (II) upon heating forms a cream-colored material; such discoloration detracts from its utility where clarity is required. U.S. Pat. No. 3,522,329 discloses a random copolymer prepared from the (a) salt of diamine of polyethylene oxide [HOCH.sub.2 CH.sub.2 (O-CH.sub.2 CH.sub.2).sub.n ] and adipic acid and (b) .epsilon.-caprolactam (also called caprolactam). U.S. Pat. No. 3,514,498 discloses a random copolymer prepared from the (a) salt of diamine of polyethylene oxide and adipic acid and (b) .epsilon.-caprolactam.
Examples of block copolymers are as follows. The previously mentioned U.S. Pat. No. 3,514,498 also discloses a block (random) copolymer prepared from two polymers: (a) polymer resulting from the salt of diamine of polyethylene oxide and adipic acid and .epsilon.-caprolactam and (b) poly-.epsilon.-capramide (nylon-6). U.S. Pat. No. 3,549,724 also discloses a block (random) copolymer prepared from (a) polymer prepared from polyethylene oxide diammonium adipate and .epsilon.-caprolactam and (b) nylon-6 or nylon-6,6. U.S. Pat. No. 3,160,677 discloses a block copolymer prepared from (a) a polymer prepared from dibutyloxalate [COOC.sub.4 H.sub.9).sub.2 ] and a diamine and (b) polycaprolactam.
Contrary to expectations based on the previously discussed art it has now been found that it is possible to prepare a composition comprising a copolymer of blocks of polyamide and random poly(dioxa-amide) having moisture uptake equivalent to that of cotton. In addition, fibers of the copolymer have overall fiber properties substantially equivalent to that of such nylons as nylon-6.